EP0060587B1 - Procédé d'agglomération pour la fabrication de détergents granulaires - Google Patents

Procédé d'agglomération pour la fabrication de détergents granulaires Download PDF

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Publication number
EP0060587B1
EP0060587B1 EP19820200251 EP82200251A EP0060587B1 EP 0060587 B1 EP0060587 B1 EP 0060587B1 EP 19820200251 EP19820200251 EP 19820200251 EP 82200251 A EP82200251 A EP 82200251A EP 0060587 B1 EP0060587 B1 EP 0060587B1
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EP
European Patent Office
Prior art keywords
alkali metal
added
dispenser cup
process according
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19820200251
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German (de)
English (en)
Other versions
EP0060587A3 (en
EP0060587A2 (fr
Inventor
Robert R. Ziek
Stephen E. Schuh
Robert A. Staab
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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Publication date
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Publication of EP0060587A2 publication Critical patent/EP0060587A2/fr
Publication of EP0060587A3 publication Critical patent/EP0060587A3/en
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Publication of EP0060587B1 publication Critical patent/EP0060587B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C11D3/062—Special methods concerning phosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • This invention relates to a process for making a granular detergent product. More particularly, the invention relates to a process for preparing detergent compositions which are useful in automatic dishwashing machines.
  • compositions comprising in combination an alkali metal polyphosphate such as sodium tripolyphosphate, alkaline salts such as sodium silicate and sodium carbonate, a surfactant and a chlorine containing compound that provides hypochlorite ion in solution have particular utility for machine dishwashing.
  • alkali metal polyphosphate such as sodium tripolyphosphate
  • alkaline salts such as sodium silicate and sodium carbonate
  • a surfactant and a chlorine containing compound that provides hypochlorite ion in solution
  • a chlorine containing compound that provides hypochlorite ion in solution
  • U.S. Patent 2,895,916 discloses an order of addition in which chlorinated trisodium phosphate is added to the composition only after the aqueous silicate has been added to an anhydrous polyphosphate. A carton caking benefit is said to result from a more rapid hydration of the sodium tripolyphosphate in the absence of chlorinated trisodium phosphate.
  • 4,169,806 discloses an order of addition in which a portion of the nonionic surfactant is mixed with one or more of the dry ingredients other than a major part of the sodium tripolyphosphate, and another portion of the surfactant is added to the major part of the sodium tripolyphosphate concurrent with or subsequent to the addition of the agglomerating agent to the sodium tripolyphosphate.
  • an agglomerated granular detergent composition comprising from 15% to 50% of sodium tripolyphosphate, from 5% to 25% silicate solids wherein the average SiO,:M 2 0 weight ratio is from 1.0 to 3.6, M being an alkali metal, from 2% to 12% of a low-foaming nonionic surfactant in which process a particulate mixture of anhydrous sodium tripolyphosphate, solid alkali metal silicate and optionally alkali metal sulfate and carbonate are blended in a mixer, the mixture is agitated with an agglomerating agent comprising water and with the low foaming nonionic surfactant, the agglomerated product then being discharged from the mixer wherein from 2% to 20% of a dispenser cup caking inhibitor is added during said agitation after at least 30% of said agglomerating agent has been added to said particulate components, said dispenser cup caking inhibitor being selected from one or more alkali metal chlorides,
  • the process of the invention is carried out in apparatus suitable for the mixing of dry particulate components and adapted so that liquid components such as water or an aqueous alkali metal silicate solution agglomerating agent can be sprayed on or otherwise added to a bed or falling curtain of one or more particulate components during the mixing operation.
  • Any suitable mixing device such as an inclined pan agglomerator, a rotating drum or any other vessel with suitable means of agitation may be used. Methods of agitating, mixing and agglomerating particulate components are well known to those skilled in the art.
  • the apparatus may be designed or adapted for either continuous or batch operation so long as the essential process steps can be achieved.
  • Optional process steps include screening of particulate materials before processing, screening or grinding the composition to any desired particle size, addition of optional ingredients such as an alkali metal dichlorocyanurate bleach and sodium carbonate, and allowing the final composition to come to equilibrium with respect to temperature and hydration before packing into cartons.
  • optional ingredients such as an alkali metal dichlorocyanurate bleach and sodium carbonate
  • the theoretical basis for the unexpected improvement in dispenser cup caking resistance provided by incorporation of the dispenser cup caking inhibitor is believed to be at least partially related to the complex hydration characteristics of anhydrous sodium tripolyphosphate.
  • This compound has different hydration characteristics depending on its method of manufacture.
  • a so-called Form I is produced if the process of manufacture includes a relatively high temperature calcination step.
  • a Form II results when lower temperatures are employed.
  • Form I is characterized by relatively rapid hydration characteristics.
  • Form II particularly in the absence of any substantial level of Form I material, is slow to hydrate, but has a greater immediate solubility.
  • Commercially available sodium tripolyphosphate is generally a mixture of Form I and Form II.
  • U.S. Patents 2,622,068, 2,961,409 and 2,961,410 disclose the hydration characteristics of Form I and Form II sodium tripolyphosphate in the manufacture of spray-dried detergents.
  • the process of this invention applies to granular detergent compositions comprising the following essential ingredients: (1) sodium tripolyphosphate; (2) alkali metal silicate; (3) a low-foaming nonionic surfactant; and (4) an alkali metal salt dispenser cup caking inhibitor.
  • the detergent compositions made by the process of the invention contain sodium tripolyphosphate at a level of from 15% to 50% and preferably from 25% to 45% by weight.
  • Anhydrous sodium tripolyphosphate comprises all or a part of the particulate components contacted with the agglomerating agent in the process of the invention.
  • the sodium tripolyphosphate can be in granular form such that at least 90% is retained on a 100 Tyler mesh screen or in powdered form such that at least 90% passes through a 100 Tyler mesh screen.
  • Optional polyphosphates useful in the practice of the invention are the water-soluble sodium and potassium salts of pyrophosphoric acid (H 4 P 2 0 1 ) and polymeric metaphosphoric acid (HP0 3 )n.
  • the value of n is typically below 50 in the interest of water solubility.
  • the sodium and potassium salts or metaphosphoric acid are often designated "glassy" phosphates and exist as a series of polymers. Glassy phosphates may also be represented by the formula (M 2 0)m(P 2 0 5 )n wherein M is an alkali metal, n is in the range of from 5 to 50 and m:n is in the range of 1:1 to 1:1.5 on a molar basis.
  • An example of a glassy phosphate is sodium hexametaphosphate (Na 6 P 6 0 18 ).
  • the alkali metal silicate The alkali metal silicate
  • compositions made by the process of this invention contain alkali metal silicate solids at a level of from 5% to 25% on an anhydrous weight basis and having an average Si0 2 :M 2 0 weight ratio of from 1.0 to 3.6, M being an alkali metal.
  • a sodium silicate having a weight ratio of SiO 2 :Na 2 0 of from 1.6 to 3.3, most preferably from 2 to 3.2.
  • Lower ratio silicates which are relatively more alkaline provide good cleaning performance but in order to provide protection to materials such as aluminum and china, it is desirable to have at least 10% and up to 75% of the Si0 2 present at a Si0 2 :Na 2 0 ratio above 3.0.
  • Aqueous alkali metal silicate solutions used as agglomerating agents preferably contain at least 45% water.
  • Silicate solids can be added dry in anhydrous or hydrous form.
  • Preferably at least a portion of the total silicate is hydrous silicate mixed with sodium tripolyphosphate before the addition of an agglomeration agent.
  • compositions made by the process of this invention contain from 2.0% to 12% of a low-foaming nonionic surfactant by weight.
  • a preferred level of surfactant is from 3.0% to 8.0%.
  • the surfactant is an alkoxylated nonionic surfactant and preferably the composition is essentially free of sulfonated or sulfated anionic surfactants.
  • nonionic surfactants examples include:
  • Preferred surfactants are those having the formula RO-(C 2 H 4 0),,R' wherein R is an alkyl or alkylene group containing from 17 to 19 carbon atoms, x is a number from 6 to 15, preferably from 7 to 12, and R 1 is selected from hydrogen, C 1 - s alkyl groups, C 2 - s acyl groups and groups having the formula ⁇ (CyH 2y O) n H wherein y is 3 to 4 and n is a number from 1 to 4.
  • low sudsing compounds of (4), the other compounds of (5), and C 17 - 19 materials of (1) which have a narrow ethoxy distribution.
  • compositions made by the process of the invention contain from 2% to 20%, preferably from 4% to 15%, of a dispenser cup caking inhibitor selected from one or more alkali metal chlorides, lithium sulfate, sodium orthophosphate, citrate or acetate.
  • a dispenser cup caking inhibitor selected from one or more alkali metal chlorides, lithium sulfate, sodium orthophosphate, citrate or acetate.
  • Operative dispenser cup caking inhibitors are in the form of dry powders having a particle size such that at least 80% passes through a 35 Tyler mesh screen (mesh size 0.422 mm).
  • the dispenser cup caking inhibitor is added during the process of the invention after at least 30%, preferably 75%, and most preferably 90%, of the water or aqueous sodium silicate agglomerating agent has been added to the particulate components comprising sodium tripolyphosphate.
  • An especially preferred material is sodium chloride having a particle size such that at least 80% passes through a 100 Tyler mesh screen (mesh size 0.152 mm).
  • the process of the invention employs either water or an aqueous sodium silicate solution as the agglomerating agent.
  • the finished compositions will contain water in the form of hydrated salts, preferably from 9% to 12% by weight.
  • Sodium or potassium dichlorocyanurate is optionally but preferably incorporated in the compositions in an amount sufficient to provide available chlorine equal to from 0.75% to 2.5% by weight of the composition.
  • a preferred material is sodium dichlorocyanurate dihydrate as disclosed in U.S. Patent 3,936,386, which provides 56% available chlorine by weight.
  • available chlorine The ability of a compound to provide hypochlorite ion in solution is generally measured as "available chlorine".
  • the available chlorine reflects the method of producing an inorganic hypochlorite (e.g., Available chlorine is the chlorine liberated by acidification of a solution of hypochlorite ions and at least a molar equivalent amount of chloride ions.
  • the usual analytical method of determining available chlorine in a solution is addition of an excess of an iodide salt and titration of the liberated free iodine with a reducing agent.
  • the process of the invention utilises alkali metal carbonate to provide the alkalinity needed for optimum cleaning performance.
  • Alkali metal carbonates particularly sodium carbonate
  • the product sudses too much, to incorporate one of the many suds-suppressing ingredients disclosed in the above mentioned patents at a level of from 0.01% to 10%, preferably from 0.05% to 3%.
  • the preferred suds suppressing materials are mono- and distearyl acid phosphates; the self-emulsified siloxane suds suppressors of U.S. Patent 4,126,045, and mixtures thereof.
  • Organic sequestering builders such as citrates and nitrolotriacetates can be present in the compositions, but preferably at levels no greater than 10% by weight. The presence of organic builders tends to hurt the performance of these compositions by leaving visible spots and filming on glassware.
  • China protecting agents including aluminosilicates, aluminates, etc., can be present in amounts up to 5%, preferably from 0.2% to 2%.
  • Filler materials sodium sulfate in particular, to control product density and other physical characteristics can also be present in amounts up to 60%, preferably not more than 30% by weight.
  • Dyes, perfumes, crystal modifiers and the like can also be added in minor amounts.
  • This solution also contained minor amounts of perfume and dye.
  • compositions were packed in airtight containers pending evaluation. Resistance to automatic dishwasher dispenser cup caking was measured as indicated in the table below.
  • Composition A was superior to Composition B in resistance to dispenser cup caking. No Composition A remained in the dispenser cup at the end of the rinse cycle, the point of principal notice of dispenser cup caking.
  • Example I-A The process of Example I-A was repeated with the substitution of NaCI having a particle size such that 80% passed through a 35 Tyler mesh screen (mesh size 0.422 mm) and less than 20% passed through a 100 Tyler mesh screen (mesh size 0.152 mm).
  • the resultant composition was superior to Composition B of Example I but slightly inferior to Composition A of Example I.
  • composition B of Example I The materials listed in the table below were added to Composition B of Example I at the levels and process cycle time indicated. 300 grams of each resultant composition was mixed with 100 grams of 37°C distilled water and stirred in a 400 ml beaker. Viscosity of the product slurries was measured by a Brookfield spindle viscometer (No. 4 spindle/6 rpm) after seven minutes.
  • All dispenser cup caking inhibitor materials listed above had a particle size such that at least 80% by weight passed through a 100 Tyler mesh screen (mesh size 0.152 mm).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (6)

1. Procédé pour préparer une composition de détergent granulaire aggloméré comprenant de 15% à 50% de tripolyphosphate de sodium, de 5% à 25% de solides de silicate, dans lequel le rapport pondéral moyen Si02:M20 est de 1,0 à 3,6, M étant un métal alcalin, de 2% à 12% d'un tensio-actif non ionique à faible moussage, procédé dans lequel on mélange dans un mélangeur un mélange particulaire de tripolyphosphate de sodium anhydre, du silicate de métal alcalin solide et éventuellement du sulfate et du carbonate de métal alcalin, on agite le mélange avec un agent d'agglomération comprenant de l'eau et avec le tensio-actif non ionique à faible moussage, le produit aggloméré étant ensuite déchargé du mélangeur, procède caractérisé en ce qu'on ajoute de 2% à 20% d'un inhibiteur d'agglutination en gobelet de distributeur, pendant ladite agitation après addition d'au moins 30% dudit agent d'agglomération à ces composants particulaires, l'inhibiteur d'agglutination en gobelet de distributeur étant choisi parmi un ou plusieurs chlorures de métaux alcalins, le sulfate de lithium et l'orthophosphate, le citrate ou l'acétate de sodium, et étant une matière sèche présentant une dimension particulaire telle qu'au moins 80% traversent un tamis de 0,422 mm d'ouverture de mailles.
2. Procédé selon la revendication 1, dans lequel l'inhibiteur d'agglutination en gobelet de distributeur est le chlorure de sodium.
3. Procédé selon l'une des revendications 1 et 2, dans lequel l'inhibiteur d'agglutination en gobelet de distributeur présente une dimension particulaire telle qu'au moins 80% traversent un tamis de 0,152 mm d'ouverture de mailles.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel l'inhibiteur d'agglutination dans le gobelet de distribution est est ajouté après addition d'au moins 75% dudit agent d'agglomération auxdits composants particulaires.
5. Procédé selon l'une quelconque des revendications 1 à 4, qui comprend en outre l'étape consistant à ajouter un dichlorocyanurate de métal alcalin au produit aggloméré pour donner une proportion de chlore disponible comprise de 0,5% à 3% du poids de la composition.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le tensio-actif non ionique à faible moussage comprend un composé ayant pour formule
Figure imgb0005
dans laquelle R est un groupe alkyle ou alkylène contenant de 17 à 19 atomes de carbone, x est un nombre valant de 6 à 15 et R1 est choisi parmi un atome d'hydrogène, des groupes alkyles en Ci à C5, des groupes acyles en C2 à C5, et des groupes de formule
Figure imgb0006
dans laquelle y vaut 3 à 4 et n vaut de 1 à 4.
EP19820200251 1981-03-13 1982-03-01 Procédé d'agglomération pour la fabrication de détergents granulaires Expired EP0060587B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US24328181A 1981-03-13 1981-03-13
US243281 1981-03-13

Publications (3)

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EP0060587A2 EP0060587A2 (fr) 1982-09-22
EP0060587A3 EP0060587A3 (en) 1983-06-29
EP0060587B1 true EP0060587B1 (fr) 1986-07-02

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DE (1) DE3271854D1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19801085A1 (de) * 1998-01-14 1999-07-15 Henkel Kgaa Homogene Tensidgranulate für die Herstellung von stückigen Wasch- und Reinigungsmitteln

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4169806A (en) * 1978-08-09 1979-10-02 The Procter & Gamble Company Agglomeration process for making granular detergents
DE2925137A1 (de) * 1979-06-22 1981-01-08 Keri Dipl Ing Karoly Homogene, staubfreie und rieselfaehige wasch- und reinigungsmittelgranulate, sowie verfahren zu deren herstellung

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CA1173323A (fr) 1984-08-28
DE3271854D1 (en) 1986-08-07
EP0060587A3 (en) 1983-06-29
EP0060587A2 (fr) 1982-09-22

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